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Synthesis and modification of monodisperse polymer particles for chromatography
Umeå University, Faculty of Science and Technology, Chemistry.
2008 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Liquid chromatography is an analytical technique that is constantly facing new challenges in the separation of small molecules and large biomacromolecules. Recently the development of ultra high pressure liquid chromatography has increased the demand on sturdy particles as stationary phase. At the same time the particle size has decreased to sub-2 µm and packed into shorter analytical columns. This thesis deals with the development of new ways of preparing particulate polymer materials using divinylbenzene (DVB) as crosslinker. It includes a novel procedure for synthesizing monodisperse polymer particles by photoinitiated precipitation polymerization. A 150 W short arc xenon lamp was used to initiate the polymerizations. The synthesized particles are monodisperse and have an average particle size ranging from 1.5 to 4 μm depending on reaction conditions and have subsequently been used as grafting templates. The surface of DVB particles contains residual vinyl groups that serve as anchoring points for further functionalization via a variety of grafting schemes. Copolymerization with incorporation of 2,3-epoxypropyl methacrylate yielded pendant oxirane groups on the particle surface. Atom transfer radical polymerization (ATRP) was used to graft methacrylates from the surface resulting in a core-shell type material. A “grafting to” scheme was used to attach pre-made sulfopropyl methacrylate telomers onto particles containing oxirane rings.

Abstract [sv]

Populärvetenskaplig sammanfattning på svenska:

Vätskekromatografi är en analytisk kemisk teknik som ständigt står inför nya utmaningar när det gäller att separera allt från små organiska föreningar till stora makro¬molekyler. Denna avhandling beskriver tillverkning av polymera partiklar med exceptionellt jämn storleksfördelning och ytmodifiering av dessa, för användning som stationärfas i kromatografi¬kolonner. Polymeriserings¬tekniken som används är utfällnings¬polymerisering där lösningen UV-bestrålas av en 150 W xenonlampa. Monomeren (byggstenen) löses tillsammans med en intiator i ett lösningsmedel och efterhand som polymeriseringen fortskrider faller polymerpartiklarna ut. Polymerpartiklarna är gjorda av monomeren divinylbensen som fungerar som en tvärbindare, dvs att den länkar ihop flera kedjor till ett hårt litet nystan. Partiklarna växte till en storlek på 1,5 till 4 µm under två till fyra dygn.

Efter tillverkningen är partiklarnas yta täckta av vinylgrupper som kan användas för att fästa funktionella polymerkedjor. Genom att tillföra monomeren 2,3-epoxipropyl¬metakrylat i polymeriseringen kunde man desutom få en partikelyta som innehöll epoxigrupper. Epoxigrupperna användes för att fästa positivt laddade polymerkedjor av bestämd längd. Materialet packades i en kromatografikolonn och användes för att separera en testlösning bestående av fyra proteiner.

Partiklarna användes även som bas för ymppolymerisering där den vinyltäckta ytan fått reagera med vätebromid. Detta gör att partiklarna blir stora makroinitiatorer som kan användas för att på ett kontrollerat sätt låta polymerkedjor växa från ytan. I en undersökning ympades 2,3-epoxypropylmetakrylat från ytan på partiklarna och resultatet blev ett tjockt ytskikt. Epoxigrupperna kunde sedan hydrolyseras till dioler vilket gjorde partiklarna mer hydrofila.

Place, publisher, year, edition, pages
Umeå: Kemi , 2008. , 45 p.
Keyword [en]
Polymer particles; photoinitiation; precipitation polymerization; styrene; divinylbenzene; atom transfer radical polymerization; liquid chromatography
National Category
Analytical Chemistry
Identifiers
URN: urn:nbn:se:umu:diva-1948ISBN: 978-91-7264-709-1 (print)OAI: oai:DiVA.org:umu-1948DiVA: diva2:142531
Public defence
2009-01-23, KB3A9, KBC-huset, Linneaus väg, Umeå Universitet, Umeå, 10:00 (English)
Opponent
Supervisors
Available from: 2008-12-18 Created: 2008-12-18 Last updated: 2009-11-20Bibliographically approved
List of papers
1. Monodisperse Polymeric Particles by Photoinitiated Precipitation Polymerization
Open this publication in new window or tab >>Monodisperse Polymeric Particles by Photoinitiated Precipitation Polymerization
2007 (English)In: Macromolecules, ISSN 0024-9297, E-ISSN 1520-5835, Macromolecules, Vol. 40, no 6, 1962-1968 p.Article in journal (Refereed) Published
Abstract [en]

Monodisperse polymer particles consisting of DVB and styrene-copoly-DVB were successfully synthesized by photoinitiated precipitation polymerization with 2,2'-azobis(2-methylpropionitrile) (AIBN) as initiator. A focused 150 W xenon short arc lamp was used to radiate the sample mixtures. The size of the particles ranged from 1.5 to 4 m and could be varied by changing the monomer concentration between 2 and 10% (v/v) and by means of the time of polymerization. By using photoinitiation instead of thermal initiation, it was possible to avoid coagulum and arrive at spherical particles with an exceptionally high monodispersity for particles of this size range (polydispersity index < 1.02) and with monomer loadings well above 5%.

Identifiers
urn:nbn:se:umu:diva-12365 (URN)doi:10.1021/ma061826+ (DOI)
Available from: 2007-04-03 Created: 2007-04-03 Last updated: 2017-12-14Bibliographically approved
2. Polymerization of Divinylbenzene and Divinylbenzene-co-Glycidyl Methacrylate Particles by Photoinitiated Precipitation Polymerization in Different Solvent Mixtures
Open this publication in new window or tab >>Polymerization of Divinylbenzene and Divinylbenzene-co-Glycidyl Methacrylate Particles by Photoinitiated Precipitation Polymerization in Different Solvent Mixtures
(English)Manuscript (preprint) (Other (popular science, discussion, etc.))
Identifiers
urn:nbn:se:umu:diva-3705 (URN)
Available from: 2008-12-18 Created: 2008-12-18 Last updated: 2010-01-14Bibliographically approved
3. Hydrobromination of residual vinyl groups on divinylbenzene polymer particles followed by atom transfer radical surface graft polymerization
Open this publication in new window or tab >>Hydrobromination of residual vinyl groups on divinylbenzene polymer particles followed by atom transfer radical surface graft polymerization
2009 (English)In: Journal of Polymer Science Part A: Polymer Chemistry, ISSN 0887-624X, E-ISSN 1099-0518, Vol. 47, no 5, 1259-1265 p.Article in journal (Refereed) Published
Abstract [en]

Rigid and monodisperse spherical polymer particles with 2.36 ± 0.18 m diameter containing residual surface vinyl groups were prepared by photoinitiated precipitation polymerization of divinylbenzene. Anti-Markovnikov addition of HBr to the surface vinyl groups yielded a 2-bromoethyl functionality that was used as macroinitiator for atom transfer radical polymerization (ATRP), providing the possibility for further functionalization by controlled grafting from processes. This was demonstrated by grafting of glycidyl methacrylate brushes from the particle surface, using an ATRP system based on CuBr and pentamethyl diethylenetriamine. Existence of a methacrylic overlayer was verified by FTIR and XPS measurements, and the grafted particles were easily dispersed in water, confirming conversion of the particle surface from hydrophobic to hydrophilic. Hydrobromination of residual vinyl groups yields a macroinitiator that can be used for grafting of glycidyl methacrylate by ATRP.

Place, publisher, year, edition, pages
Wiley Periodicals, Inc., A Wiley Company, 2009
Keyword
atom transfer radical polymerization (ATRP), chromatography, divinylbenzene, grafting, living radical polymerization (LRP), photoinitiation, polymer particles, precipitation polymerization
National Category
Other Basic Medicine
Identifiers
urn:nbn:se:umu:diva-18274 (URN)10.1002/pola.23209 (DOI)
Available from: 2009-02-02 Created: 2009-02-02 Last updated: 2017-12-14Bibliographically approved
4. A cation-exchange material for protein separations based on grafting of thiol-terminated sulfopropyl methacrylate telomers onto hydrophilized monodisperse divinylbenzene particles
Open this publication in new window or tab >>A cation-exchange material for protein separations based on grafting of thiol-terminated sulfopropyl methacrylate telomers onto hydrophilized monodisperse divinylbenzene particles
2008 (English)In: Journal of Separation Science, ISSN 1615-9306, E-ISSN 1615-9314, Vol. 31, no 12, 2143-2150 p.Article in journal (Refereed) Published
Abstract [en]

A strong cation-exchange separation material has been prepared from monodisperse divinylbenzene particles modified by a grafting to approach, utilizing as anchoring points epoxy groups introduced onto the surface of the particles via oxidation of residual vinyl groups. The grafted chains consisted of thiol-terminated telomers of sulfopropyl methacrylate prepared by iniferter mediated polymerization, and grafting was performed by reaction of the corresponding thiolate anion with the surface epoxy groups. Attachment through epoxy moieties that were subsequently converted into 2,3-propanediol groups increased the hydrophilicity of the polymeric particles and incubation experiments showed no signs of the proteins denaturing on the column during an extended contact time of 1 h at room temperature. The performance of the grafted material was demonstrated by the chromatographic separation of cytochrome C, lysozyme, myoglobin, and ribonuclease A, in a cation-exchange mode.

Keyword
Grafting to, Photoinitiation, Polymeric particles, Protein separation, Precipitation polymerization
Identifiers
urn:nbn:se:umu:diva-10270 (URN)doi:10.1002/jssc.200800180 (DOI)18615833 (PubMedID)
Available from: 2008-08-06 Created: 2008-08-06 Last updated: 2017-12-14Bibliographically approved

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